Processes of removing anions from liquids



Patented May 10, 1949 PROCESSES OF REMOVING AN IONS FROM LIQUIDS Lennart A. Lundberg, Stamford, Conn., assignor to American Cyanamid Company, New York,

N. Y a corporation of Maine No Drawing. Original application October 25,

1945, Serial No. 624,606. Divided andtliis application October 25,1945, Serial No.'624,607

6 Claims. (01. 210-44) This invention relates to resins suitable for the removal of anions from fluid media and to processes of purifying fluid media by means of such resins.

An object of the present invention is'to provide a resinous material which is insoluble in water and which is suitable for removing anions from water and other fluid media.

Another object of the present invention is to prepare an anion active resin from an hydroxy aliphatic polyhalide and a polyamine.

A further object of the present invention is to provide a process of producing resinous materials suitable for the removal of anions from fluid media.

These and other objects are attained by condensing an aliphatic polyhalide which contains an hydroxy group in beta positionitoeach of the halogens with an alkylene polyamine.

Still another object of the present invention is to provide an improved process for removing anions from water and other fluid'media.

This object is attained by contacting a fluid containing anions with an insoluble resin prepared in the manner described above.

The following examples in which the proportions are in parts by weight are given by way of illustration and not in limitation.

Example 1 Parts Glycerol dichlorohydrin (17.5 mols) 2,258 Tetraethylenepentamine (10 mols) 1,890 Water 6,000 Sodium hydroxide (10 mols) 400 The tetraethylenepentamine is charged into a suitable reaction vessel provided with an agitator and a steam jacket or other means of heating and 5000 parts of water are added thereto. The re-v sulting solution is heated and the glycerol dichlorohydrin added rapidly to the hot agitated solution.

After this addition is complete, the mixture is heated forv about 1.5 hours. A clear solution, which becomes opaque on cooling due to the separation of an oily Phase, results. The chilled syrup is transferred to another vessel, similarly equipped with heating means, and the sodium. hydroxide dissolved in 1000 parts of water is added. The resulting mixture is heated and gel ation occurs with a slight evolution of heat within 5 minutes. a

The opaque, orange-colored, firm gel is broken up into small pieces, placed in trays and cured in an oven at a temperature of about 95-105 C.

for about 17-18 hours. The cured resin is ground and screened, and the 20-40 mesh material is placed in a suitable bed through which water containing 0.004 N sulfuric acid and 0.002 N HCl is passed; The resin removes the acid from the water and its capacity is found to be 15.9 kilograins (hereinafter abbreviated kgrs.) of calcium carbonate per cubic foot of resin. The resin has a density of about 8.4 lbs/cu. it.

Example 2 Parts Glycerol dichlorohydrin (20 mols) -1- 2,580 Tetraethylenepentamine (10' mols) 1,890 Water 6,000 Sodium hydroxide (15 mols) 600 V Exampleii The procedure of Example 2 may be modified somewhat and the preparation oi the resin carried out as a two-step process. 1613 parts of the glycerol dichlorohydrin (12.5 mols) is first added to the hot agitated solution of tetraethylenepentamine in 4500 parts of water. The aqueous mixture is heated for about 1.5 hours, and the resulting solution transferred to another vessel and cooled to about 25 C. A solution of the sodium hydroxide in 1500 parts of water is added with stirring and then the remaining 968 parts (7.5 mols) of glycerol dichlorohydrin is introduced.- The mixture is heated by steam and gelation occurs within 5 minutes. Although this reaction is more exothermic than that resulting from the unmodified process of Example 2, the gels are similar in appearance. g

The gel obtained according to the two-step process of this example was granulated, cured, ground and screened as described in Example 1.

- The resulting resin h'asa capacity for removing anions of about 20.6 kgrs. of calcium carbonate per cubic foot of resin and a density of about 9.9 lbs/cu. ft.

The sodium hydroxide is dissolved in 2000 parts of water and the procedure of Example 1 is followed. Aresin is produced having a capacity for removing anions which varies from about 17.2 kgrs. to about 26.9 kgrs. of calcium carbonate per cubic foot of resin. The density of the resin may vary from about 12.1 to about 15.9 lbs/cu. ft.

Example 5 600 parts (15 mols) of sodium hydroxide in 3750 parts of water is charged into a suitable vessel and heated by steam. The glycerol dichlorohydrin is added slowly, with agitation, over a fifteenminute period after which the mixture is heated an additional minutes. The syrup is then transferred to another vessel, cooled to about 60 C., and 800 parts (20 mols) of sodium hydroxide in 1500 parts of water added. After heating, a nonhomogeneous, orange-brown, opaque gel is formed within 10 minutes. This gel is treated in the same manner as those of the other examples, the resulting resin having a density of about 10.6 lbs./cu. ft. and a capacity of removing anions from the solution equivalent to about 12.9 kgrs. of calcium carbonate per cubic foot of resin.

Example 11 Parts Melamine (10 mols) 1,260 Concentrated hydrochloric acid (10 mols) 365 I Water 6,360 Epichlorohydrin (30 mols) 2,774 Tetraethylenepentamine (7.5 mols) 1,420 Sodium hydroxide (20 mols) 800 Example 6 Parts Glycerol dichlorohydrin (30 mols) 3,870 Tetraethylenepentamine (10 mols) 1,890 Water 8,000 Sodium hydroxide mols) 1,400

The sodium hydroxide is dissolved in 2000 parts of water and the substances are reacted as in Example 1 to produce a resin having a capacity for removing anions equal to about 21.5 kgrs. of calcium carbonate per cubic foot of resin and a density of about 12.3 lbs./ cu. ft.

Example 7 Example 8 Parts Glycerol dichlorohydrin (35 mols) 4,515 Tetraethylenepentamine (10 mols) 1,890

Water 10,650 Sodium hydroxide mols) 1,800

The sodium hydroxide is dissolved in 2650 parts of water andthe one-step procedure of Example 1 is followed. The resin produced in this manner has a capacity of about 20.5 kgrs. calcium carbonate per cubic foot of resin and a density of about 12.0 lbs./cu. it.

Example 9 Parts,

Glycerol dichlorohydrin (45 mols) 5,805 Tetraethylenepentamine (10 mols) 1,890 Water 9,950 Sodium hydroxide mols) 2,600

The sodium hydroxide is dissolved in "3350 parts of water and the substances are reacted as in Example 1 to produce a resin having a density of about 23.8 lbs/cu. it. Its capacity is equivalent to about 18.5 kgrs. of calcium carbonate per cubic foot of resin.

Example 10 Parts Glycerol dichlorohydrin (25 mols) 3,225 Diethylenetriamine (10 mols) 1,030 Water 5,250 Sodium hydroxide (35 mols) 1,400

A solution consisting of diethylenetriamine and To a slurry consisting of the melamine, hydrochloric acid and water is added the epichlorohydrin over a period of about 45 minutes while heating the mixture over an oil bath maintained between C. and C. The temperature of the reaction mixture remains at about 94 C.

throughout the addition but rises slowly to about 100 C. shortly after completion. The reaction mixture is heated for an additional half hour, filtered to remove slight traces of insoluble material, and the filtrate cooled. A glass-like material believed to be tris-(3-chloro-2-hydroxypropyl) melamine hydrochloride separates.

; The tetraethylenepentamine is added to the hydrochloride and an exothermic reaction ensues, the temperature rising gradually to about 40 C. The slurry which is strongly basic is heated by means of steam until a neutral, slightly viscous syrup is obtained. The syrup is cooled to 50C. and the sodium hydroxide added. The temperature rises rapidly to about. 83 C. and then subsides so heating is resumed for about an hour at the end of which time the orange-colored gel is broken up and cured in the usual manner.

Other polyalklyene polyamines may be substituted for part or all of those used in the preceding examples. Furthermore, mixtures of two, three, four, five, seven or any other number of polyamines may be employed. Minor molar proportions of the polyalkylene polyamine may be replaced with ammonia or monoor polyamines other than the alkylene polyamines. Preferably, however, polyalkylene polyamines are employed exclusively.

Examples of suitable polyamines include 1,3- diaminopropane, 1,4-diamino-n-butane, 1,3-diamino-n-butane, 1,5-diamino-n-pentane, 1,6-diamino-n-hexane, 1,10-diamino-n-decane, 1,6-diamino-3-methyl-n-hexane, 3,3'-diamino dipropyl ether and other similar diamines containing hetero atoms in the chains separating the amino groups, triethylene tetramine.. pentaethylene hexamine and all of the higher homologs thereof containing additional CH2CH2NH groups in the chain between the primary amino groups, etc. Complex mixtures of polyethylene polyamines of high molecular weight obtained by the addition of large numbers of molecules of ammonia to ethylene dibromide or ethylene dichloride and the like may be used.

com

dichlorohydrin (1,3-dichloro-propanol-2) to-the polyamine be at least about 1.5:1 when the two substances are brought together in order to ob-v tain insoluble resins. There is no maximum amount of dichlorohydrin which maybe used but generally it should not exceed a molar r'atioof 5:1 or with polyamines having more than flve amino groups the ratio should not be greater than 1 mol of dichlorohydrin for each amino group in the polyamine. While proportions of dichlorohydrin larger than those mentioned may be used it desired, it will generally be undesirable since this will ordinarily reduce the capacity of the re-. sulting resins. On the other hand, the .use of higher ratios of dichlorohydrih to polyamine may be advantageous for economic reasons.

The addition of a strong alkali, such as sodium hydroxide, is desirable. When glycerol di'schlorohydrin condenses with tetraethylenepentamine, hydrochloric acid is set free and if a neutralizing agent for that hydrochloric acid is not, provided, the condensation proceeds very slowly. on the other hand, the use of alkali in large quantities is undesirable since the water-soluble content of the resins appears to depend; for the most part, upon the amount of alkali used in the preparation of the resin. The sodium chloride formed when the hydrochloric acid is neutralized by sodium hydroxide is dissolved out of the resin ,when the resin is placed in water, and thus the structural rigidity of the product is reduced. Any

strong alkali may be used which will not congroup in beta position to each halogen-are suittabie for reaction with polyamines'in accordance with this invention to produce. anion active resins.

Some of these. polyhalides are, for example:

Corresponding compounds with other halogens mercially. but the present invention is replaced in oi the present invention. i chlorine compounds are cheaper and'niore' readily obtainable than the others and hence-more attractive comnot intended to be rystricted thereto. I

A minor p, portion of the polyhalidesmay be reaction with a polyamine by the -chioro-beta, gamma-epoxy organic compounds described and claimed in the copending application of James R. Dudley and Lennart A.Lund-. berg, Serial'No. 616,644 flied September 15,1945, and/or by the polyepoxy compounds disclosed and "claimed in the James R. Dudley application Serial No. 655,005 filed March 16, 1946,

The condensation of the polyhalide and pohramine may becarried out in the presence of any desired solvent which does not react with-the reactants or the reaction products such as water,

It is immaterial whether-all the polyhalide' be introduced at once or whether itbe introduced stepwise, since the corresponding resins obtained methanol, ethanol, the monomethylor monoethyl-ethers' oi ethylene glyc'ol,--etc. While it is convenient to add the polyhalide to the polyamine, the order or addition may be reversed.

' diiiiculties such as rapid boiling of the reaction such as, for example, bromine or iodine in place of the chlorine may also be used in'the process mixture, loss of the reactive materials by vaporization, etc. In other. words, the reaction temperature is not critical and therefore, the temperature may be varied from about 0 C. up to about C. or even higher.

' It is believed, and I do not wish to be limited to any particular theory of the mechanism of the reaction between the hydroxy polyhalides and polyamines, that epichlorohydrin or another alpha-chloro-beta, gamma-epoxy compound is first formed from'the 'polyhalide. and that it in turn reacts with'the polyamine. Regardless of the mechanism, the final products closely resemble in physical properties and operating characteristics'those resins prepared directly from an epichlorohydrin-type compound and a polyamine.

Since the resinous materials formed in accordance with this invention are condensation products, the curing of the resins is by condensation. Inasmuch as hydrochloric acid is; set free, alkali may be added aspointed out heretofore to absorb excess acid. The heat treatment which is given heat, although other conditions may be used ineluding temperatures from 50. up 0. or higher.

The anion active'resins maybe activated or reto about generated by means-of dilute alkaline solutions,

such as for example, (Ll-10% aqueous solutions of sodium hydroxide, sodium carbonate, etc.

It is preferable to grind and screen the resins to a Particle size of from about a-so mesh. Use of larger particles causes channeling, and smaller particles of resin have been found to pack, thus 7 reducing the anion exchange efllciency ot.the material.

The resinous materials produced in accordance with this invention are suitable for the removal of all kinds of acids and anions in general from fluid media. a They may be used to extract the strong mineral acids (preferably in relatively low concentrations), organic acids such as acetic acid. oxalic acid, etc., from water and organic liquids. The anions of salts such as chloride ion,from ammonium chloride, or a sulfate ion from .ammonium sulfate may be removed by means the resinous products described herein. p

The anion active resins are useful for many purposes, examples of which are the removal of acid from water, the removal of acid from alcoholic solutions, the purification of sugar juices, the purification of pectin, the removal of acid from aqueous formaldehyde solutions, etc. While the resins are especially suitable for the removal of anions from aqueous media, they may be used to extract acids or anions from fluid media other than water, and they may even be used for the extraction of acids from gases. The resins may be used as absorbents for plant nutrients and as such may be used as a media for growing plants or as a means for applying nutrients to the soil.

To be sufilciently insoluble for practical use in, the water purification art resins should have a sufllciently low solubility that it will not dissolve very rapidly by the solution to be treated. Thus, water should not dissolve more than 1 part of resin in 1000 parts of water when passed through a bed of resin (after the first cycle comprising an activation, exhaustion and reactivation of the resin).

This application is a continuation-in-part of the James R. Dudley and Lennart A, Lundberg application Serial No. 616,644 filed September 15,.

1945, and a division of my copending application Serial No. 624,606 filed 0ctober 25, 1945.

Obviously manymodifications'and variations in the processes and compositions described herein may be made without departing from the spirit and scope of the invention as defined in the appended claims.

I claim:

1. A process which comprises contacting a liquid medium containing anions with a water-insoluble granular resinous material obtained by a process comprising the steps of bringing together at least one alkylene polyamine and glycerol dichlorohydrin, permitting the resulting condensation product to gel, curing the resulting gel by heating, and granulating the cured gel, said granular resinous material being of such low water solubility thatwater will not dissolve more than one part of resin in 1,000 parts of waterwhen it is passed through a bed of resin after a first cycle comprising an activation, an exhaustion and a reactivation of the resin, and separating said medium from said material. 2. A process as in claim 1 wherein said liquid medium is an aqueous medium.

3. A process as in claim lwherein said polyamine is a polyethylene polyamine.

4. A process as in claim 1 wherein said polyamine is a tetraethylene-pentamine.

5. A process which comprises passing an aqueous medium containing anions through, and in contact with, a bed of a water-insoluble granular resinous material obtained by a process comprising the steps of bringing together at least one alkylene polyamine and glcerol dichlorohydrin, permitting the resulting condensationproduct to gel, curing the resulting gel by heating, andgranulating the cured gel, said granular resinous material being of such low water-solubility that water will not dissolve more than one part of resin in 1,000 parts of water when it is passed through curing the resulting gel by heating, and granulating the cured gel, said granular resinous material being of such low water-solubility that water will not dissolve more than one part of resin in 1,000 parts of water when it is passed through a bed of resin after a. first cyclecomprising an activation, an exhaustion, and a reactivation of the resin.

LENNART A. LUNDBERG.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,104,092 Munz et a1. Jan. 4, 1938 2,223,930 Griessbach et a1 Dec. '3, 1940 2,228,514 Griessbach et al. Jan. 14', 1941 2,354,172 Myers et a1 July 18, 1944 FOREIGN PATENTS Number Country Date 694,991 Germany -1 Aug. 13, 1940 Certificate of Correction Patent No. 2,469,694 May 10, 1949 LENNART A. LUNDBERG It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 3, line 65, for 23.8 lbs./cu. ft. read 12.8 lbs./cu. ft.;

and that thesaid'Lettei-s Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 20th day of December, A. D. 1949.

THOMAS F. MURPHY,

Am'stant G'ommz'ssz'oner of Patents. 

